Chlorinated rubber emulsion



Patented Mar. 20, 1945 2,311,399 omoamlrrnn RUB ER EMULSION Julius G. Little, Wilmington, Del., assisnor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Application March 29, 1941, Serial N0. 385,860

7 Claim.

This invention relates to aqueous emulsions of mixtures of chlorinated rubber and a glycol ester of arosin acid.

The glycerol ester of rosin, usually. referred to as ester gum, has assumed great importance in many industrial fields. The glycol esters of rosin, however, although they have been described in the literature, have achieved practically no commercial utilization. The glycol esters of rosin are generally softer and lower melting that the glycerol esters and consequently are not adapted to many of theester gum uses.

I have found that glycol esters of rosin act both as a plasticizer and as a resin in conjunction with chlorinated rubber and thereby provide compositions which are quite unique 'and which are highly valuable.

It is, therefore, 'an object-of this invention to M. Norman.

provide aqueous emulsions containing as essen-' tial constituents, chlorinated rubber and a. glycolester of a rosin acid. .It is a further objector this invention to provide aqueous emulsions which on application to tetraethylene glycol,'hexaethylene glycol, nonaethylene glycol, decamethylene glycl, butylene glycol, dipropylene glycol, etc.,- or mixtures thereof, etc. The glycol esters of the rosin acids or rosins may be prepared by procedures wellknown in the art. The diethylene glycol ester,

for example, may be prepared by heating together approximately equivalent proportions of rosin and diethylene glycol in. accordance with the process of U. S. Patent 1,779,710 to George 7 By a preferable method of preparation, 231 parts by weightof N-wood rosin and 42 parts by weight of diethylene glycol may be heated at a temperature gradually increased from 200, up to 285?- C. in a 6-7 hour period and the heating maintained at that point for an ad-- ditional 7-8 hours. The resulting ester will have an acid number .of about 6-8, amelting point (Hercules drop method) of about 48 to 51 C. and will be pale in colon. An esterification catalyst such as, for example, boric acid, zinc, etc,

. may be used-to accelerate the esteriflcation'. The

a. surface and after evaporation of the solvent,

will leave deposited on such surface the unique, combined mixture comprising essentially chlorinated rubber in combination with a glycol ester of a rosin acid.

New, in accordance above objects are accomplished by emulsifying a solution of chlorinated rubber and a glycol ester of a rosin acid in water by means of a suitable emulsifying agent.

The glycol esters of a fosin acid which may be utilized in preparing the novel compositions of this invention are characterized by complete thermoplasticity and high flexibility. They are essentially water-insoluble and have melting points varying in the range of about C. to about 70 0., depending on the particular glycol or mixtureof glycols used in theesterification.

The rosin acid useful in-preparing compositions of this invention may be in the form of purified rosin acids or may be in the form of the rosin itself. liflther wood rosin or gum rosin such as American or French gum rosin may be used. The acids derived from such rosins, for

example, abietic acid, pimaric acid, sapinic acid,

etc, are all contemplated. The rosin or rosin acidmay also be hydrogenated before esteriilcation with the glycol.

The glycols which may be employed inpre-v with this invention, the

reaction is preferably carried out in an inert atmosphere. In a similar manner the ethylene glycol ester of rosin may be prepared by heating approximately equivalent proportions of rosin and ethylene glycolgradually to a temperature of about 250 C. in a period of about 3'hours, and-maintaining the heating at that temperature until the "desired acid number is reached. :By'

heating at 250 C. for about 5 hours, for example, the ester will have an acid number of about 33 and a melting point (Hercules drop method). of

paring useful rosin esters may be-any one or a.

mixture of, for example, ethylene. fl ycol, propylthe known procedures and will comprise the about 69 C.

The propylene glycol ester of rosin may be prepared in a 8 higher temperature. Thus, for example, N-wood rosinrnay' be heated with an amount of. propylene glycol equivalent to about.30% excess of the equivalent amount at. a temperature raised gradually from 220 up to about 270 (3., and held at that point until the desired acid number is obtained. The propylene glycol ester will have a melting point of about 65 C.

By using hydrogenated rosins or rosinacids, in i preparing the glycol esters, esters resembling those from'the untreated rosins in most properties are obtained. Generally speaking, the esters of hydrogenated" rosin will be slightly lower melting. They will also be more light-resistant. 4

The chlorinated rubber which is useful in providing the novel compositions in accordance withthis invention may be prepared by any of ene glycol, diethylene glycol, triethylene glycol, P ducts containingirom-abolut to about armanner or at a slightlyviscosity types may be utilized such as those having viscosities up to about 7000 centipoises. As solvents for the chlorinated rubber and glycol ing or sizing of textile fabrics, yarns, etc., where they provide softer finishes with good flexibility and high resistance to laundering. The emulsions also exert a desirable'binding action on other finemulsions may also be used directly inthe finishester of rosin any of the well-known water-imishing agents. miscible solvents for these materials may be em- As illustrative of the various aqueous emulsions 'ployed, as for example, coal tar hydrocarbons which may be prepared in accordance with this such as benzene, toluene, xylene; petroleum hyinvention, the following examples are typical: drocarbonssuchas Stoddard solvent, Solvesso v Example I No. 2 and No; 3, butanol, etc., or mixtures thereof. By Stoddard solvent and the Solvesso sol- A Solution Of 125 P ts by e ht of Chlorinated vents are meant the petroleum hydrocarbons ubb r d 5 P ts by weight of t e d ei y known in the industry as such and generally ene y l e ter f hydro en woo r sin w characterized as follows: prepared in 250 parts by weight of a 1:1 mixture 15 of toluene and xylene. The solution obtained was Boiling Specific emulsified by addition to 250 parts by weight of a e gravity water containing 5 parts by weight of sodium I oleate. The emulsion was .then homogenized by two passes through a Premier colloid mill. The S3f223::3j:311 iii??? d2; finished emulsion had a solids content'of 33.8% Solvesso No.3 175-210 0.884 by weight I Example I! Suitable emulsifying agents for use i preparing the emulsions are, for example, the alkali metal A similar emulsion was prepared according to salts of the higher aliphatic half ester sulfates, 'the procedure of Example I but utilizing a soluas sodium lauryl sulfate, sodium stearyl sulfate; tion of 125 parts of chlorinated rubber and 40 sulfonated oils, as sulfonated castor oil, sulfonparts of the diethylene glycol ester of hydroated olive' oil, etc.; soaps, as sodium stearate, genated wood rosin in a. solvent composed of 125 sodium oleate, potassium. oleate; sulfonic acids, parts by weightof toluene and 115 parts by weight as sodium butyl naphthalene sulfonate, sodium 3" of xylene. The emulsion was prepared by disisopropyl naphthalene sulfonate, etc. persing the above solution in a solution of 5 parts The proportion of the glycol ester of a rosin by weight of sodium oleate in 200 parts by weight acid to be used with the chlorinated rubber will of water. An emulsion having a solids content of depend'generally on the particular type of com- 27.8% by weight resulted. position desired and the particular glycol used Example I in preparing the ester. Generally speaking, the glycol ester of a rosin acid will be present in .an The emulsion of Example I was duplicated t, itm range of ut 20 t about use of the diethylene glycol ester of N wood rosin 80% by weight based on the weight of the chloin p a of the hydrogenated $08111 ester- A Simirinated rubber, and preferably within the range 40 emulsion resultedof about 33% to about 67% by weight based on The emulsions prepared according to the above the weight of'chlorinated rubber. examples were used in the preparation-of print- Where desirable other materials such as waxes, ing pastes having highly advantageous properoils, pigments, fillers, etc. may be included in the ties in the printing of textile fabrics. As illusemulsions. Anwadditional plasticizer may also trative of such an application of the emulsions be employed where a particular eflect may be the printing pastes listed below in Table I were desired. Such additional ingredients may deprepared.

- Table I Sample No.

- p 253st? tilt? 1%? 2353.?" will tilt Emulsion of Example I Emulsion of Example 11. 50 50 Emulsion oi Example III- 50 60 Tim-barium sulphate pigment 20 20 20 20 20 20 Blue pulp color (50% in water) 4 4 4 sirably be dissolved in the solvent before emulslno The printing pastes were prepared according fication. to the formulae listed above in Table I by add- The aqueous emulsions produced in accordance ing the pigment to the emulsion with stirring. with this invention are highly useful for a large The emulsion reversed in each case and the visvariety of purposes. Thus, they may be combined cosity showed an appreciable rise. The pastes with pigments ordyes to provide printing pastes 55 were all of satisfactory consistency for printing for printing textiles. With pigments or dyes, the fabrics from intaglio rolls. I combination of the chlorinated rubber and the Each of the printing pastes shown in Table I glycol ester of rosin exerts a superior binding were printed on cloth, the cloth then air dried action on the pigment or color and thereby profor 24 hours and subsequently dried at 100 C. for vides a .print which exhibits excellent resistance 5 minutes. ,The cloth was dampened and ironed to washing, crocking and dusting out. In the dry in about 2 minutes at a temperature of about surface coating of paper,- cellulose foils, metal, 2'75 to 300 F. The prints obtained were still! and glass, wood, cloth, leather, etc., the emulsions crisp and were highly desirable where a print may be used to impart highly desired efiects. The having such properties is desired, such as in 7 printing of canvas. awning cloth, etc.

Other uses of the aqueous emulsions produced in accordance with this invention will be readily apparent.

It will be understood that the details and specific examples are illustrative only and the inven tion as herein broadly described and claimed is in no way limited thereby.

This application forms a continuation-impart of my application, Serial No. 285,959, filed July 22, 1939, entitled Composition of matter.

What I claim and desire to protect by Letters Patent is:

1. An aqueous emulsion comprising a solution of chlorinated rubber and a glycol ester of a rosin acid having only glycol and rosin acid as reacted components of the ester and having a melting point within the range of about 25 C. to about 70 C. in a Water-immiscible solvent therefor emulsified in water containing an emul' sifying agent.

2. Anaqueous emulsion comprising a solution of chlorinated rubber and from about, 20 to about 80 per cent by weight based on the weight of chlorinated rubber of a glycol ester of arosin acid having only glycol and rosin acid as reacted components of the ester and having a melting point within the range of about 25 C. to about 70 C.

in a. water-immiscible solvent therefor, said solution being emulsified in water containing an emulsifying agent.

3. An aqueous emulsion comprising a solution 4. An aqueous emulsion comps a solution of chlorinated rubber d from about 33 to about fill per cent by weight based on the weight of chlorinated rubber or a glycol ester oia rosin acid having only glycol and rosin acid as reacted components of the ester and having a melting point wi the range of! about 25 C. to about to C. in a cible solvent therefor, said solution being emulsified in water contalning an emulsifying agent.

5. An aqueous emulsion comprising a solution of chlorinated rubber and from about so to about alt-per cent by weight based on the weight of chlorinated rubber of a diethylene glycol ester of hydrogenated rosin having only the said glycol and the said rosin as reacted components or the ester and in a water-immiscible solvent therefor, said solution being emulsified in water conof chlorinated rubber and from about 20 to about 80 per cent by weight based on the weight of; chlorinated rubber of a diethylene glycol ester of a rosin acid having only glycol and rosin acid as reacted components of the ester and'in a waterimmiscible solvent therefor, said solution being emulsified in water containing an emulsifying agent.

taining an emulsifying agent.

6. An aqueous emulsion comprising a solution of chlorinated rubber and trom'about 20 to about per cent by weight based on the weight of chlorinated rubber of a diethyleneglycol ester of wood rosin having only the said glycol and the said rosin as reacted components of the ester and in a water-immiscible solvent therefor, said solution being emulsified in water containing an emulsifying agent.

'7. An aqueousemulsion comprising a solution of chlorinated rubber and from about 20 to about 80 per cent by weight based on the weight of chlorinated rubber of a diethylene glycol ester of gum rosin having only the said glycol and the said rosin as reacted components of the ester and in awater-immiscible solvent therefor, said emulsifying agent.

JULIUS G. HTTLE. 

